Phosphonamide plant growth regulants

ABSTRACT

The disclosure teaches a group of carbamoylphosphonamidates can be used to retard the growth of plants. The carbamoylphosphonamidates of this invention are prepared as follows. An appropriate amine is reacted with a halogenated phosphite. The product is treated with a suitable halogenated carboxylic acid ester followed by treatment with ammonia or a suitable amine.

United States Patent [191 Jelinek Jan. 21, 1975 PHOSPHONAMIDE PLANT GROWTH REGULANTS [76] Inventor: Arthur Gilbert Jelinek, 2500 Lindell Rd., Wilmington, Del. 19808 [22] Filed: Oct. 19, 1972 [21] Appl. N0.: 299,093

Related US. Application Data [63] Continuation-impart of Ser. No. 79,252, Oct. 8,

1970, Pat. No, 3,712,936.

[52] US. Cl 71/76, 71/86 [51] Int. Cl. A0ln [58] Field of Search 71/86, 76

[56] References Cited UNITED STATES PATENTS 3,627,507 12/1971 Langdorfijr. ..71/86 Primary ExaminerJames 0. Thomas, Jr.

[57] ABSTRACT The disclosure teaches a group of carbamoylphosphonamidates can be used to retard the growth of plants.

4 Claims, No Drawings PHOSPHONAMIDE PLANT GROWTH REGULANTS CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of my copending application Ser. No. 79,252, filed Oct. 8, 1970, now US. Pat. No. 3,7l2,936.

SUMMARY OF THE INVENTION This invention relates to a novel group of carbamoylphosphonamidates, the method of using thecarbamoylphosphonamidates to modify plant growth patterns and formulations containing the carbamoylphosphonamidates which are useful in plant modification applications.

The compounds of this invention are represented by the following formula:

where R is alkyl of from one to eight carbon atoms, chloroalkylof from one to eight carbon atoms containing up to three chlorine atoms, bromoalkyl of from one to eight carbon atoms containing up to three bromine atoms, alkoxyalkyl of from three to ten carbon atoms, alkenyl of from two to eight carbon atoms, alkynyl of from three to four carbon atoms, phenyl of benzyl;

R is hydrogen, alkyl of one tofour carbon atoms, hy-

droxyalkyl of two to four carbon atoms, alkenyl of three to four carbon atoms, or alkynyl of three to four carbon atoms;

R is hydrogen, alkyl of one to four carbon atoms, hy-

droxyalkyl of two to four carbon atoms, alkenyl of three to four carbon atoms, or alkynyl of three to four carbon atoms; or R, and R can be taken together to form a bridge consisting of --(CH O-(CI-I or (CI-1 where n is 4, 5, or 6; and one of R and R can be R is hydrogen, alkyl of one to four carbon atoms or alkenyl of three to four'c'arbon atoms; and

R is hydrogen, alkyl of one to four carbon atoms or alkenyl of three to four carbon atoms.

Of the above compounds of formula 1, those compounds where R is alkyl of one to four carbon atoms or alkenyl of two to four carbon atoms, R and R are each hydrogen and R and R are each hydrogen or alkyl of one to four carbon atoms are preferred because of their outstanding activity.

This invention also relates to the method of modifying the growth rate of plants which comprises applying an effective amount of'a compound of formula (I) to a plant to effect modification of the growth of said plant, particularly retardation of the growth rate of treated plants, especially that of woody vegetation.

This invention further relates to agricultural formulations consisting of a compound of formula (1) in combination with suitable agricultural adjuvants and modifiers.

DESCRIPTION OF THE INVENTION This invention is founded on the discovery that the compounds of formula l) are useful for modifying the growth rate of plants. In this regard, it has been noted that the compounds of this invention, as represented by formula l are particularly useful to retard the growth rate of plants. The compounds of this invention are particularly useful to retard the growth of woody plants. The compounds of this invention can, therefore, be applied in areas such as power line rights-of-way where low-growing and slow-growing vegetation is especially desirable. They are useful to control the growth and Preparation The carbamoylphosphonamidates of this invention are readily prepared by the interaction of an appropriate amine with a halogenated phosphite followed by 4 5 treatment with an appropriate halogenated carboxylic -N acid ester and then ammonia or an amine.

\ R6 These reactions can be represented as follows:

R R OR R (2) Cl-P(OR) 2 NH----- N-P NH- cl R4 R1; OR R Cl-C-X-R n P-C-AR R-C] Ru 4 OR n 0 i O 0 N-P-C--X--R \Imufi 9 t n I N-P-C-N RTXH R2; OR R2 R! Q i It where R and R are the same or different and are hydrogen or alkyl of one through four carbon atoms;

In the above equations, R, R R R and R are defined as above. R is lower alkyl, preferably methyl or ethyl. X is oxygen or sulfur. Normally, X will be oxygen, in the above described reaction, however, when the amine in equation 4 has relatively low reactivity, X is preferably sulfur. More information relative to the reaction when X is sulfur can be had by reviewing the disclosure of US. Pat. No. 3,005,010.

The starting materials of equation 2, above, are commercially available or can be readily prepared using methods known to the art. The reaction of equation 2 is run at approximately C. and involves a slow addition of the amine to a solution of the dialkyl chlorophosphite in an inert solvent. Suitable solvents include ethers, hydrocarbons or chlorinated hydrocarbons.

The phosphoramidite ester intermediates are generally liquids and may be purified by distillation under reduced pressure after removal of the amine hydrochloride by-product and the solvent. Illustrative of the dialkyl chlorophosphite esters which can be employed in the reaction are dimethyl chlorophosphite, diethyl chlorophosphite, diallyl chlorophosphite, bis-( 2- chloroethyl) chlorophosphite, and dioctyl chlorophosphite.

Illustrative of the amines useful in the above reaction are methylamine, diethylamine, diallylamine, butylamine and isopropylamine.

In the procedure outlined in reaction 3 the phosphoramidite ester is treated with a chloroformate or chlorothiolformate at a temperature of from -l0C. to 100C. In this reaction, a solvent is not necessary, although one can be used if desired and when a solvent is used that solvent should be inert to the reactants employed. Solvents suitable for use in this reaction include ethers and hydrocarbons. The carbonylphosphonamidate ester intermediates generally are liquid products. Many times, it is not necessary to purify them further after removal of the by-product alkylhalide, however, if necessary, purification can be carried out by distillation at reduced pressure. Illustrative of the acid chlorides employed in the above reaction are methyl chloroformate, ethyl chloroformate, methyl chlorothiolformate and ethyl chlorothiolformate.

Illustrative of the phosphoramidite ester intermediates which can be used as a starting material in reaction 3 are dimethyl N-methylphosphoramidite, diphenyl N- methylphosphoramidite, diethyl N,N-diethylphosphoramidite, dimethyl N,N-dipropylphosphoramidite and bis(2-chloroethyl) N,N-dimethylphosphoramidite. The procedure of reaction 4 is conducted at a temperature of from 0C. to 25C. The reaction can be run with or without a solvent present. Suitable solvents include water, ethers, hydrocarbons or chlorinated hydrocarbons. Illustrative of the amines which can be employed in reaction 4 are methylamine, dimethylamine, ethylamine, allylamine, l,l-dimethylhydrazine, morpholine and pyrrolidine.

Illustrative of the carbonyl phosphonamidate ester intermediates which can be employed in reaction 4 are allyl methoxycarbonyl-N-methylphosphonamidate, methyl methoxycarbonyl-N-N-dimethylphosphonamidate, ethyl methoxycarbonyl-N,N-diethylphosphonamidate, 2-chloroethyl ethoxycarbonyl.-N,N- dimethylphosphonamidate, butyl methoxycarbonyl- N,N-diethylphosphonamidate, isopropyl methoxycarbonyl-N,N-dimethylphosphonamidate and octyl methoxycarbonyl-N,N-dimethylphosphonamidate.

The following are illustrative of the carbamoylphosphonamidates of this invention:

Ethyl Carbamoyl-N,N-diethylphosphonamidate Allyl .Carbamoyl-N,N-dimethylphosphonamidate Ethyl Carbamoyl-N,N-dimethylphosphonamidate 2-Chloroethyl Carbamoyl-N,N-dicthylphosphonamidate Methyl Carbamoyl-N,N-diallylphosphonamidatc Isopropyl Dimethylaminocarbamoyl-N.N-dimcthylphosphonamidate Ethyl MethyIcarbamoyl-N-methylphosphonumidatc The compounds of formula (I) generally are liquids. but some are solids. In general, the compounds prepared according to the methods described above are acceptable for use as plant growth regulants after removal of the by-product alcohol and solvent, although if further purification is desired, the solid products can be recrystallized from an appropriate solvent and those products of this invention which are liquid can be distilled under high vacuum.

Those compounds of formula (1) containing shortchain substituents in general have good solubility in water, lower alcohols and ketones. Those compounds of formula (1) with longer chain substituents exhibit decreased solubility in water, but have increased solubility in most organic solvents. The differences in physical properties can be employed to advantage in the preparation of various types of agricultural formulations as will be illustrated below.

The following examples are presented to further illustrate this invention. In the example, parts and percentages are by weight unless otherwise specified.

EXAMPLE 1 One hundred parts of diethyl chlorophosphite are dissolved in 640 parts of anhydrous diethyl ether and treated slowly with 102 parts of diethylamine with the reaction temperature maintained at 0C. After stirring an additional hour at 0C., the mixture is warmed to 25C. and the diethylamine hydrochloride is removed by filtration. Evaporation of the solvent and distillation of the residue affords parts of diethyl N,N-diethylphosphoramidite, b.p. 6973/9.2 mm.

Eighty-five parts of the above liquid are cooled to l0C. and treated dropwise with 42 parts of methyl chloroformate over a 3-hour period. The mixture is slowly warmed to 100C. The temperature is maintained until gas evolution ceases. Distillation of the mixture gives 55.4 parts of ethyl methoxycarbonyl- N,N-diethylphosphonamidate, b.p., -92/0.5 mm.

Ten parts of the above liquid are treated with 18 parts of a 29 percent solution of ammonia in water at 0. After 30 minutes the solution is evaporated under reduced pressure affording 8 parts of essentially pure ethyl carbamoyl-N,N-diethylphosphonamidate m.p. 98lO1C.

EXAMPLES 2-44 The procedure of Example 1 is repeated, substituting a stoichiometric quantity of the indicated Dialkyl chlorophosphite, the First Amine and the Second Amine" to produce the Carbamoyl Product. Alternatively, the methyl chloroformate can be replaced by a stoichiometric quantity of methyl chlorothiolformate when it is advantageous to do so.

5 6 Ex. Dialkyl Chlorophosphite First Amine Second Amine Carbamoyl Product 2 dioctyl chlorophosphite dimethylamine ammonia octyl carbamoyI-N.N-dimethylphosphonamidate 3 bisl4-(2-chloro)octyl] methylamine ammonia 4-(2-chloro)octyl earbanioyl-N l p phne methylphosphonnmidate 4 bts[4-(l,2,3-trichloro) methylamine ammonia 4-l l.Z.3-trich|oro)octyl cnrhaimoyloctyllchlorophosphite N-methylphosphonnmidntc 5 dipropargyl chlorophosphite dimethylamine ammonia propargyl czirhamoylN.NdEmcthyI- phosphonamidate 6 dimethyl chlorophosphite diethylamine butylamine methyl butylcarhamoyl-N.N-dietliyl- I phosphonamidnte 7 bis[4-(2-bromo)octyl] diethylamine ammonia 4-(2-bromo)octyl carhnmoyLNN- chlorophosphite diethylphosphonamidate 8 bis[4-( l ,2,3-tribromo)octyl] diethylamine ammonia 4-( l.Z,3-tribromo)octyl carhamoylchlorophosphite N,N-diethylphosphonamidate 9 bis(2-chloroethyl) chlorodiethylamine methylamine Z-chloroethyl .methylcairbamoy'h phosphite N.N-diethylphosphonumidate l bis(2,2,2-trichloroethyl) diethylamine ammonia 2.2.2trich|oroethyl carbamoylchlorophosphite N,N-diethylphosphonamidate l l bis(2-chloroethyl) chlorodiethylamine ammonia 2-chloroethyl carbamoyl-NN- phosphite diethylphosphonamidate l2 bis(2,2,2-tribromoethyl) diethylamine ammonia 2,2,2-tribromoethyl carbamoylchlorophosphite N,N-diethylphosphonamidate l3 bis(2-methoxyethyl) chlorodimethylamine ammonia 2methoxyethyl carbamoyl-N,N-

phosphite dimethylphosphonamidate l4 bis[-(2-ethoxy)octyl] dimethylamine ammonia 4-(2-ethoxy)octyl carbamoyl-N,N-

chlorophosphite dimethylphosphonamidate l diallyl chlorophosphite diethylamine dimethylamine allyl dimethylcarbamoyl-N,N-

diethylphosphonamidate l6 bis(4-oct-2-enyl) chlorodiethylamine ammonia 4-oct-2-enyl carbamoyl-N,N-

phosphite diethylphosphonamidate l7 bis(3-butynyl) chlorodiethylamine ammonia 3-butynyl carbamoyl-N,N

phosphite diethylphosphonamidate 18 diphenyl chlorophosphite dimethylamine ammonia .phenyl carbamOyI-NN-dimethyl' phosphonamidate l9 dibenzyl chlorophosphite dimethylamine ammonia benzyl carhamoyl-NN-dimethylphosphonamidate 20 diethyl chlorophosphite dimethylamine dimethylamine ethyl dimethylcarbamoyl-N,N-

dimethylphosphonamidate 2l diethyl chlorophosphite diethylamine diethanolamine ethyl his(2-hydroxyethyl)earbamoyl- N,N-diethylphosphonamidate 22 diethyl chlorophosphite diethylamine 2aminopropanol ethyl 2-(1hydroxy)propylcarbamoyl- N,N-diethylphosphonamidate 23 diethyl chlorophosphite diethylamine allylamine ethyl allylcarbamoyl-N,N-diethylphosphonamidate 24 diethyl chlorophosphite diethylamine methallylamine ethyl methallylcarbamoyl-N,N-

, diethylphosphonamidate 25 diethyl chlorophosphite dimethylamine but-2-ynylamine ethyl but-2-ynylcarbamoyl-N,N-

dimethylphosphonamidate 26 diethyl chlorophosphite diethylamine azetidine ethyl lazetidinylcarbonyl-NN- diethylphosphonamidate 27 diallyl chlorophosphite diethylamine pyrrolidine allyl l-pyrrolidinylcarbonyl-N,N-

' diethylphosphonamidate 28 diethyl chlorophosphite dimethylamine morpholine ethyl l-morpholinylcarhonyl-N,N-

dimethylphosphonamidate 29 diethyl chlorophosphite dimethylamine piperidine ethyl l-piperidinylcarhonyI-N,N-

dimethylphosphonamidate 3U diisopropyl chlorophosphite diethylamine l,l-dimcthylisopropyl dimethylaminocarhamoylhydrazine N,N'diethylphosphonamidate 31 diethyl chlorophosphite dimethylamine butylhydrazine ethyl hutylaminocarhamoyl-N,N-

dimethylphosphonamidate 32 diethyl chlorophosphite dibutylamine ammonia ethyl carbamoyl-N,N-dibutylphosphonamidate 33 diethyl chlorophosphite butylamine ammonia ethyl carbamoyl-N-butylphosphonamidate 34 diethyl chlorophosphite methylamine methylamine ethyl methylcarbamoyl-N-methylphosphonamidate 35 diallyl chlorophosphite dimethylamine isopropylamine allyl isopropylcarbamoyl-N,N-

, dimethylphosphonamidate 36 dimethyl chlorophosphite diallylamine ammonia methyl carbamoyl-N,N-diallylphosphonamidate 37 diethyl chlorophosphite dimethallylammonia ethyl carbamoyl-N,N-dimethallylamine phosphonamidate 38 diallyl chlorophosphite dimethylamine ammonia allyl carbamoyl-N,N-dimcthylphosphonamidate 39 diethyl chlorophosphite dimethylamine ammonia ethyl carbamoyl-NN-dimethyh phosphonamidate 40 dimethyl chlorophosphite butylamine ammonia methyl carbamoyl-N-butylphosphonamidate 41 diisopropyl chlorophosphite dimethylamine dimethylamine isopropyl dimethylcarbamoyl-N,N-

dimethylphosphonamidate 42 dimethyl chlorophosphite diethylamine ammonia methyl carbamoyl-NN-diethylphosphonamidate 43 dimethyl chlorophosphite dimethylamine ammonia methyl carbamoyl-N.N-dimethylphosphonamidate 44 diisopropyl chlorophosphite diethylamine ammonia isopropyl carbamoyl-N,N-diethylphosphonamidate Formulation namtc acid) can be included in the compositions of this As stated above, one aspect of this invention relates to a formulation containing a compound of formula l in combination with pest control adjuvants or modifiers to provide compositions in the form of dusts, water soluble powders, solutions, granules or pellets. In addition, other plant growth modifying agents such as maleic hydrazide and Alar" (N-dimethylaminosucciinvention in combination with the compounds of this invention.

Compositions of the invention, may contain as a conditioning agent one or more surface-active agents, sometimes called surfactants, in amounts sufficient to render a given composition containing the compounds of this invention readily dispersible in water or capable of wetting foliage efficiently.

The surfaceactive agent used in this invention can be a wetting, dispersing or an emulsifying agent which will assist dispersion and solution of the active compound. The surface-active agent or surfactant can include such anionic, cationic and non-ionic agents as have heretofore been generally employed in plant control compositions of similar types. Suitable surface-active agents are set forth, for example, in Detergents and Emulsifiers 1968 Annual by John W. McCutcheon, Inc.

In general, less than 10 percent by weight of the surface-active agent will be used in compositions of this invention and ordinarily the amount of surface-active agents will range from l5 percent but may even be less than 1 percent by weight.

Additional surface-active agents can be added to the formulations to increase the ratio of surfactantzactive ingredient up to as high as 5:1 by weight. Such compositions may have a greater effectiveness than can be expected from a consideration of the activity of the components used separately. When used at higher rates, it is preferred that the surfactant be present in the range of one-fifth to five parts surfactant for each one part of active agent.

Water-Soluble Powders Water-soluble powders are compositions containing the water-soluble active material, an inert solid extender which may or may not be water-soluble, and optionally one or more surfactants to provide rapid wetting and solution. A buffer, which may also function as an extender, can be present to improve formulation stability and to control the pH of the final spray solution.

The classes of extenders suitable for the watersoluble powder formulations of this invention are the natural clays, diatomaceous earth, synthetic mineral fillers derived from silica and silicate, starch, sugar, and inorganic salts. More preferred fillers for this invention are kaolinitcs, attapulgite clay, montmorillonite clays, synthetic silicas, synthetic sodium alumina silicate, synthetic magnesium silicate, calcium sulfate dihydrate, and disodium hydrogen phosphate.

Suitable surfactants for use in such compositions are those listed by J. W. McCutcheon in Detergents and Emulsifiers 1968 Annual. Among the most preferred surfactants are the nonionic and anionic type, and those most suitable for the preparation of the dry, soluble products of this invention are solid forms of compounds known to the art as wetters and dispersants. Occasionally a liquid, non-ionic compound classified primarily as an emulsifier may serve as both wetter and dispersant.

Most preferred wetting agents are alkylbenzeneand alkylnapthalene-sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils, ethylene oxide adducts of alkyl phenols and long-chain alcohols, and their phosphate derivatives, sorbitan fatty esters and their ethylene oxide adducts, and ditertiary acetylenic glycols. Preferred dispersants are methylcellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkylnaphthalenesulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate, and sodium N-methyl-N- (long chain acids) taurates.

Wetting and dispersing agents in water-soluble compositions of this invention are usually present at concentrations up to about 5 weight percent. The inert extender then completes the formulation. Where needed, 0.1 weight percent to 1.0 weight percent of the extender may be replaced by a corrosion inhibitor or an anti-foaming agent or both.

Thus, water-soluble formulations of the invention will contain from about 25 to 95 weight percent active material, from 0 to 2.0 weight percent wetting agent, from O to 5.0 weight percent dispersant, and from ()to weight percent inert extender, as these terms are described above.

When the water-soluble powder contains a corrosion inhibitor or an anti-foaming agent or both, the corrosion inhibitor will not exceed about 1 percent of the composition, and the anti-foaming agent will not exceed about 0.5 percent by weight of the composition, both replacing equivalent amounts of the inert extender.

It will be understood that the compounds of formula (1) vary in degree of water solubility and that in some cases, such as concentrate spraying, it may be desired to use them in aqueous systems at concentrations above their solubility limit, i.e., as partially soluble wettable powders. Such use is possible provided the product has been ground sufficiently for use in the equipment and provided the spray mixture is not held so long that crystal growth leads to inseparability. In the latter case, crystallization inhibitors, such as protective colloids, can be of some help.

Solution Concentrates The aqueous solution concentrates are prepared by -mixing a water-soluble active compound of this invention with water. A portion ofthe water may be replaced with methanol, ethanol, isopropanol, ethylene glycol, cellosolve or methyl ccllosolvc. Surfactants and buffering agents can optionally be present.

These aqueous solution concentrates will contain from 15 to 50 percent of active ingredient, and from 50 to percent water or mixture of water and hydroxylated organic solvent. Surfactants, corrosion inhibitors, buffering and anti-foam agents may also be included in which case they may replace up to 10 percent of the solvent system.

Dusts Dusts are dense powder compositions which are intended for application in dry form, in accordance with the preferred compositions and methods of the invention. Dusts are characterized bytheir free-flowing and rapid settling properties so that they are not readily windborne to areas where their presence is not desired. They contain primarily an active material and a dense, free-flowing, solid extender.

Their performance is sometimes aided by the inclusion of a wetting agent, and convenience in manufacture frequently demands the inclusion of an inert, adsorptive grinding aid. For the dust compositions of this invention, the inert extender may be either of vegetable or mineral origin, the wetting agent is preferably anionic or non-ionic and suitable absorptive grinding aids are of mineral origin.

Suitable classes of inert solid extenders for use in the dust compositions are those organic or inorganic powders which possess high bulk density and are very freeflowing. They are also characterized by possessing relatively low surface areas and are poor in liquid absorption. Suitable classes of grinding aids are natural clays, diatomaceous earths, and synthetic mineral fillers derived from silica or silicate. Among ionic and non-ionic wetting agents, the most suitable are the members of the group known to the art as wetting agents and emulsifiers. Although solid agents are preferred because of ease in incorporation some liquid non-ionic agents are also suitable in the dust formulations.

Preferred inert solid extenders for thedusts of this inventionare micaceous talcs, pyrophyllite, dense kaolin clays, tobacco dust and ground calcium phosphate rock such as that known as Phosphodust, a trademark of the American Agricultural Chemical Company. q

Preferred grinding aids are attapulgite clay, diatomaceous silica, syntheticv fine silica and synthetic calcium and magnesium silicates. Preferred wetting agents are those previously described under water-soluble powder formulations. 1

The inert solid extenders in the dusts of this invention are usually present in concentrations of from about 30 to 90 weight percent of the total composition. The grinding aid will usually constitute 5 to 50 weight percent of the composition, and the wetting agent will constitute from about to 1.0 weight percent of the composition. Dust compositions can also contain other surfactants such as dispersing agents in concentrations of up to about 0.5 weight percent.

The water-soluble powders described above can also be used in the preparation of dusts. While such watersoluble powders could be used directly in dust form, it is more advantageous to dilute them by blending with the dense dust diluent. In this manner, dispersing agents, corrosion inhibitors, and anti-foam agents may also be found as components of a dust.

Thus, the dust compositions of this invention will comprise about to weight percent active material, 5 to 50 weight percent adsorptive filler, 0 to 1.0 weight percent wetting agent, and about to 90 weight percent dense, free-flowing dust diluent, as these terms are used herein. Such dust formulations can contain, in addition, minor amounts of dispersants, corrosion inhibitors, and anti-foam agents, derived from the watersoluble powders used to make the dusts.

Granules and Pellets Under some circumstances it may be. advantageous to apply the compounds of this invention in the form of granules or pellets. Suitable carriers are natural clays, some pyrophyllites and vermiculites. Wetting agents of the type listed by J. W. McCutcheon in Detergents and Emulsifiers 1967 Annual can also be present to aid leaching of the active component.

One method of preparation suitable for both granules and pellets involves blending the active ingredient with clays, water-soluble salts, surfactants and a small amount of water. After pelleting and/or granulating, the formulation is dried prior to use. A second method suitable for the preparation of granules formulation involves spraying a solution of the active material on porous, adsorptive, preformed clay or vermiculite granules. Preformed granules of organic origin, such as corn cob, are also suitable for use by this method of preparation. Surfactants listed by McCutcheon can also be included in the spray solution. After drying, the granules are ready for application.

The preferred granules or pellets will contain about 5 to 30 weight percent of active material, about 0 to 5 weight percent wetting agent and about 65 to 95 weight percent inert mineral carrier.

Paints and Dressings While the formulations described above can be used to apply the compounds of formula (1) to cut portions of plants, these compounds can also be included in paints and tree-wound dressing to be applied to local areas after pruning.

Thus, taking advantage of good water-solubility, they can be incorporated in various aqueous emulsions of asphalt or in water-based points. Aerosol paint formulations can be of the water-in-oil emulsion type, usually with organic soluble propellant and film former, or may be anaqueous system propelled by inert gas.

Alternatively, the compounds may be finely divided and dispersed in organic systems such as organic solvent based paints and varnishes. It is preferred to use relatively nonpolar solvents, such as aliphatic hydrocarbons, in such systems to prevent crystal-growth in storage. Such formulations have the disadvantage that they must be well stirred before use to insure accurate dosing. This requires some care, as relatively low levels of active ingredient are present.

Certain compounds of formula (1 particularly those having large organic substituents, have sufficient solubility in organic solvents to permit formulation in organic solutions for application to cut portions of plants. Thus, they may be incorporated into organic solvent based paints, lacquers, and varnishes at relatively low, but effective, levels. These may be of the type designed foraerosol or bough application. For this purpose halocarbon and aromatic hydrocarbon solvents are preferred, but other more polar solvents, such as ketones, alcohols, ethers, esters and amides can be included as cosolvents or as sole solvents.

Application As stated earlier, this invention is founded on the discovery that the compounds of formula (1) are useful for modifying the growth rate of plants. More particularly the compounds of this invention are useful as plant growth retardants. They also affect the flowering and fruit set of numerous plants.

The term plant growth retardant as used in this disclosure is to be understood to mean an agent which when applied to a plant or its environs will slow the growth of the plant. This also includes a delaying response on bud sprouting or prolonging of the dormancy period.

The compounds of this invention can be used to retard the growth of woody vegetation. The compounds of this invention can also be used to control the growth of turf and other herbaceous vegetations.

The compounds of this invention can be applied as foliar sprays or as soil applications to retard the growth rate of such plants or to affect flowering and fruit set.

Preferably, the compounds of this invention are applied as a foliar spray to the point of runoff although lower-volume application may also be effective.

It is preferred that the application be made while the buds for next years growth are developing, but application can also be made during the dormant stage or just after the plants have been trimmed. Or if flowering and fruit set are to be modified, the treatment is applied before, during or shortly after flowering.

It will be recognized that the rate of application is dependent upon the species to be treated and the results desired. In general, rates of from 0.25 to 20 kilograms per hectare are used although higher or lower'rates can achieve the desired effect in some instances. Preferably the composition will be applied at the rate of from 1 to 10 kilograms per hectare.

It will also be appreciated that there are a number of methods that can be used for applying the active com- 2-Chloroethyl carbamoyl-N,N-diethylphosphonamidate Methyl carbamoyl-N,N-diethylphosphonamidate Methyl carbamoyl-N,N-dimethylphosphonamidate pound to the plant. Spray application being the most 5 lsopropy] carbamoyl-N,N-diethylphosphonamidate convenient, is therefore the most commonly used Six kilograms of the above formulation are dissolved method. The compositions can be sprayed from air or in 800 liters of water and sprayed over a hectare of ground carriers. In the application of the active combrush along a railway right-of-way in August. The treatpound particular attention should be given to thorough ment has no effect on the brush the year of application, and uniform coverage of the plants treated to obtain but the next spring delays bud break and retards the the desired results. growth of the brush. Meanwhile, the grasses and other The following Examples are presented to further illow growing vegetation flourish underneath the brush lustrate the formulation and application of the comgiving a desirable green ground cover underneath. pounds of this invention. Parts and percentages in the following examples are by weight unless otherwise indi- EXAMPLE 47 cated. A wettable powder of the following formula is prepared. EXAMPLE 45 A dust having the following formula is prepared.

Ethyl carbamoyl-N,N-dimethylphosphonamidate 50.0% 4

Montmorillonite 43.0% Synthetic silica 4.0% Ethyl carbamoyl-N,N-diethylphosphonamidate 5.0% Disodium hydrogen phosphate 1.0% Talc 64.0% Sodium alkylnaphthalenesulfonate 1.0% Attapulgite 30.0% Sodium lignin sulfonute l.()% Sodium henzenesulfonate 1.0%

, The above ingredients are mixed and then ground to The active component is ground with the minor dilupass a 025 mm Screen The active ingredient in the em h Surfactant to P? scrccn- This above formulation dissolves when the composition is material is then blended with the ma or diluent to form 30 addfid to water dust compqsmon' I The following compounds can be formulated in like The following compounds of this invention can be mammn formulated m hke f- Allyl carbamoyl-N,N-dimethylphosphonamidate carbamoyl'NrN-dlmethylphosphonamldate 2,2,2-Trichloro carbamoyl-N,N-diethylphos- 2-Chloroethyl carbamoyl-N,N-diethylphosphonamiphonamidate date Propargyl carbamoyl-N,N-dimethylphosphonami- Methyl carbamoyl-N,N-d1ethylphosphonamidate date p py carbamoyl'NaNfdlethylphosphonflmidate Isopropyl carbamoyl-N,N-diethylphosphonamidate Methyl cflrbamoyl-N,N-dlallylphosphonmldate Methyl carbamoyl-N-N-diethylphosphonamidate Twenty kilograms of the above formulations was ap- 4 gctyl carbamoypMNdimethy]phosphonamidate P11ed to a POWer lme y area of PP Twenty kilograms of the above wettable powder are mately 1 hectare- (Q 1 1 p (d suspended in 1,000 liters of water and applied in early PIf-L Sweetgum q pQ y l P September to the brush growing on 1 hectare of area (Pmus PI and locust (Robmla lf f surrounding a television relay tower on top of a mounamong the predominant woody species growing in Kills min. The treatment has no effect on the brush for the area- T treatment effectlvely Yetardfid the growth remainder of the season; however, in the spring the bud rate of these plant species and reduced cost of ma nbreak is prevented or delayed, and the growth of the 'f deslrable green, low'gmwmg Vegetatlon the brush is retarded. The grasses and other low growing yvegetation are unaffected and covers the area prevent- EXAMPLE 46 mg erosion and keeping the area green. A water-soluble powder of the following formula is EXAMPLE 48 prepared. A solution of the following formula is prepared.

Allyl earbamoyl-N,Ndimethylphosphonamidate 95.0% Methyl carbamoyl-N,N-diallylphosphonamidate 24.0% Synthetic silica 3.5% Disodium hydrogen phosphate l.0% Disodium hydrogen phosphate l.0% S di laurylsulfale 05% Dioctylsodium sulfosuccinate 0.5% Water 74.5%

The above ingredients are mixed and then ground to The above components are blended to form a homopass a 0.42 mm. screen. The resulting formulation is geneous solution. water-soluble powder, with the exception of the syn- The following compounds can be formulated in like thetic silica conditioning agent. manner.

The following compounds of this invention can also be formulated in like manner.

Ethyl carbamoyl-N,N-diethylphosphonamidate Ethyl carbamoyLN,N-diethylphosphonamidate 2-Chloroethyl methylcarbamoyl-N,N-diethylphosphonamidate Methyl carbamoyl-N-butylphosphonamidate Methyl butylcarbamoyl-N,N-diethylphosphonamidate Allyl carbamoyl-N,N-dimethylphosphonamidate Ten kilograms of the above formulation are suspended in 400 liters of water and sprayed in early October on a hectare of brush growing along a steep highv EXAMPLE 49 The following wettable powder is prepared:

Ethyl carbamoyl-N,N-diethylphosphonamidate 30.0% Maleic hydrazide 20.0% Synthetic silica 2.5% Montmorillonite 45.0% Sodium alkylnaphthalene sulfonate 2.0% Partially desulfonated sodium lignin sulfonate 0.5%

The above ingredients are blended, micropulverized to a particle size essentially below 50 microns and reblended.

The following compounds can be formulated in like manner.

Allyl carbamoyl-N,N-dimethylphosphonamidate 2-Chloroethyl carbamoyl-N,N-diethylphosphonamidate Methyl carbamoyl-N,N-diallylphosphonamidate lsopropyl carbamoyl-N,N-diethylphosphonamidate Propargyl carbamoyl-N,N-dimethylphosphonamidate Octyl carbamoyl-N,N-dimethylphosphonamidate Thirty kilograms of the above formulation suspended in 400 liters are sprayed in September on a hectare of brush growing on a municipal watershed. The following spring the treatments delay or prevent bud break on the brush. The treatment does not affect low growing ground cover, therefore, the site is not exposed to erosion or excessive run-off but yields more water during the year because less is lost by transpiration from the brush.

Example 50 Ethyl carbamoyl-N-butylphosphonamidate 5% Sodium oleate 2% Water 48% Asphalt 45% Allyl carbamoyl-N,N-dimethylphosphonamidate EXAMPLE 51 The following formulation is suitable for aerosol packaging:

Methyl butylcarbamoyl-N,N-diethylphosphonamidate 2% Chloroform 50% Asphalt 25% Trichlorofluoromethane 7% Dichlorodifluoromethane 21% A solution of active ingredient and asphalt in chloroform is first prepared and the fluorocarbon propellant system then added under pressure. The finished solution is packaged in aerosol containers for use.

The following compounds can be formulated in like manner.

Ethyl carbamoyl-N,N-diethylphosphonamidate Octyl carbamoyl-N,N-dimethylphosphonamidate Propargyl carbamoyl-N,N-dimethylphosphonamidate 2,2,2-Trichloroethyl phonamidate Ethyl 1-Morpholinylcarbonyl-N,N-dimethylphosphonamidate I claim:

1. A plant growth regulant composition comprising suitable agricultural adjuvants and modifiers in combination with a compound of the formula:

carbamoyl-N,N-diethylphos- R O O 4\ H l H, 12 R2 where R is alkyl of one to four carbon atoms or alkenyl of two to four carbon atoms, R, is hydrogen; R is hydrogen; R is hydrogen or alkyl of one to four carbon atoms;

and R is hydrogen or alkyl of one to four carbon atoms. 2. A composition of claim 1 wherein the active ingredient is Ethyl carbamoyl-N,N-diethylphosphonamidate.

3. A method for retarding the growth rate of plants which comprises applying to said plants an effective amount of the compound of the formula where R is alkyl of one to four carbon atoms or alkenyl of two to four carbon atoms; R, is hydrogen; R is hydrogen; R is hydrogen or alkyl of one to four carbon atoms;

and R is hydrogen or alkyl of one to four carbon atoms. 4. The method of claim 3 wherein the compound applied is Ethyl carbamoyl-N,N-diethylphosphonamidate. 

2. A composition of claim 1 wherein the active ingredient is Ethyl carbamoyl-N,N-diethylphosphonamidate.
 3. A method for retarding the growth rate of plants which comprises applying to said plants an effective amount of the compound of the formula
 4. The method of claim 3 wherein the compound applied is Ethyl carbamoyl-N,N-diethylphosphonamidate. 